Acid cleaning and corrosion inhibiting compositions comprising gluconic acid

ABSTRACT

A biodegradable acid cleaning composition for cleaning stainless steel, and other surfaces is disclosed. The composition comprises urea sulfate in combination with gluconic acid which serves as a corrosion inhibitor. The composition retains the cleaning and corrosion prevention properties of similar phosphoric acid solutions but is safe for the environment and is less expensive to produce. Applicants have surprisingly found that the traditionally alkaline corrosion inhibitor, gluconic acid, can work effectively in an acidic cleaning composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a Divisional Application of U.S. Ser. No. 12/751,674, filed Mar.31, 2010, herein incorporated by reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to aqueous, acid cleaners for cleaningmetal and other surfaces, particularly stainless steel and forinhibiting corrosion. Methods of use and manufacturing of the same arealso disclosed.

BACKGROUND OF THE INVENTION

Steel is the generic name for a group of ferrous metals, composedprincipally of iron, which have considerable durability and versatility.By the proper choice of carbon content, addition of alloying elements,and by suitable heat treatment, different kinds of steel can be made forvarious purposes and the use in industry of all kinds of steel is nowquite expansive.

Stainless steel is defined as a steel alloy, with a minimum of 11%chromium content by mass. Stainless steel does not stain, corrode, orrust as easily as traditional steel. There are over 150 different gradesand surface finishes to allow the stainless steel to suit theenvironment in which it will be used. Stainless steel's low maintenanceand relatively low cost make it an ideal base material for manycommercial applications. It is used in cookware, cutlery, hardware,surgical instruments, major appliances, industrial equipment, it is alsoused as a structural alloy for cars and as a construction material forbuildings.

Stainless steels have a passive film of chromium oxide that forms in thepresence of oxygen due to the chromium present in the steel. This layerblocks most corrosion from spreading into the metal's internalstructure. High oxidation resistance can be achieved with chromiumadditions of 13% by weight up to 26% for harsh environments. Thechromium forms a passive layer of chromium III oxide (Cr₂O₃) whenexposed to oxygen. To have their optimum corrosion resistance, stainlesssteel surfaces must be clean and have an adequate supply of oxygen tomaintain this passive surface layer.

Cleaning of stainless steel includes the removal of various surfacecontaminants to ensure corrosion resistance, to prevent contamination,and to achieve the desired appearance of the steel. Acid cleaning is aprocess by which a solution of a mineral or organic acid in watersometimes in combination with a wetting agent or detergent or both, isemployed to remove iron and other metallic contamination, light oxidefilms, soil and similar contaminants.

Acid cleaning compositions for removing contaminants from stainlesssteel generally have the mineral or organic acid in a solution with a pHof less than 7.0. The compositions typically remove both organic (dirt,oils) and inorganic (oxides, free iron) soils in the same operation.They also are used to improve corrosion resistance and enhancebrightness of the base metal surface.

One of the problems which arises in the use of steel is its corrosion,either by the atmosphere or by the environment in which it is used. Therate of corrosion may vary, depending on the surrounding conditions andalso the composition of the steel. Stainless steel, especially, is muchmore resistant to corrosion than plain carbon and other steels. Thisresistance is due to the addition of chromium to alloys of iron andcarbon. Other metals, for example copper, and aluminum, also increasecorrosion resistance but they are limited in their usefulness. Althoughstainless steel has appreciable resistance to corrosion, it will stillcorrode in certain circumstances and attempts have been made to preventor reduce this corrosion. Most acid cleaners also include a corrosioninhibitor of some sort. For example, in acid media copper sulphate hasbeen used as a corrosion inhibitor. However this and other proposedinhibitors are not entirely satisfactory since, like copper sulphate,they may be expensive, introduce an effluent disposal problem and,moreover, are not entirely effective. For example, when coppercontaining urea sulfate solutions are placed in contact with nickelmetal, copper will plate the nickel surface.

A variety of compounds, including dialkylthioureas, such asdiethylthiourea and dibutylthiourea, are known to reduce the corrosivityof sulfuric acid to carbon steels. Thioureas are not appropriate forfood and beverage situations as any remnant thiol compounds areconsidered contamination for such surfaces.

The type of acid used has also presented problems in development of acidcleaners. Most acid cleaners are based upon phosphoric acid due to itslow cost, good combining ability with other ingredients, its ability toexert a very strong synergistic cleaning affect, and its lowcorrosivity.

Phosphoric acid has recently fallen out of favor due to environmentalconcerns. It is therefore one object of this invention to provide aphosphate free acid cleaning composition which has equal or superiorcleaning and corrosive inhibiting properties as phosphoric acid basedcleaners.

It is another object of this invention to provide aqueous, urea sulfatebased acid cleaning compositions which are relatively noncorrosive dueto addition of gluconic acid, to stainless steel and which reduce thecost of such cleaners.

Yet another object is to provide a liquid acid cleaning composition forstainless steel which is biodegradable and which includes componentswhich are generally recognized as safe.

Other objects, aspects and advantages of this invention will be apparentto one skilled in the art in view of the following disclosure, thedrawings, and the appended claims.

SUMMARY OF THE INVENTION

The present invention employs the use of gluconic acid as a corrosioninhibitor for use in acid cleaning compositions. Applicants have found,surprisingly that the combination of gluconic acid as a corrosioninhibitor in an acidic cleaning solution works well and almost prohibitsall corrosion. The invention employs an aqueous solution of a pH of lessthan 7, which uses an acid as the cleaning component. Any acid used inan acid cleaning composition may be combined with gluconic acidaccording to the invention, such as acetic acid, citric acid, oxalicacid, and sulfuric acid, all of which are traditionally used in acidcleaning compositions. In a preferred embodiment, the acid is sulfuricacid, which is more preferably combined with urea to form a urea sulfateacid cleaning composition. The acid cleaning compositions of theinvention retain the anti-corrosive properties of phosphoric acid aswell as the cleaning capabilities and are biodegradable and lessexpensive to produce.

Typical urea sulfate acid cleaners contain from about 5 to about 85,preferably about 10 to about 80 weight percent sulfuric acid; about 5 toabout 75, preferably about 10 to about 70 weight percent urea; and 0 toabout 75, usually 0 to about 50, and preferably 0 to about 25 weightpercent water. Urea and sulfuric acid, in combination, constitute atleast about 25, usually at least about 50, and preferably at least about75 weight percent of the composition, and are present in relativeproportions corresponding to urea/sulfuric acid molar ratios of morethan 2 or less than 1.

According to the invention, urea and sulfuric acid, in combination,constitute at least about 25, usually at least about 50, and preferablyat least about 75 weight percent of the composition, and are present inrelative proportions corresponding to urea/sulfuric acid molar ratios ofmore than 2 or less than 1. The gluconic acid then, can be from about0.1 up to 75% or greater of the composition, with the remainder beingwater.

Applicants have found that the level of gluconic acid to urea sulfatemust be at least greater than about 0.15% to 25% or a ratio of percentby weight of 0.012 to 1 of gluconic acid to urea sulfate. Levels lessthan this critical ratio, were found to not significantly inhibitcorrosion. There is really no upper limit on the amount of gluconic acidthat can be added to the solution, so long as the desired corrosioninhibition is achieved with the acid cleaner. The solution could evenhave a greater gluconic acid content than urea sulfate. Not only doesthe gluconic acid protect the surface of the metal from the sulfuricacid, it makes the composition less expensive and retains the lowcorrosivity and cleaning properties of phosphoric acid based cleaners.Applicants have found that addition of the corrosion inhibitor gluconicacid which was thought to only work in alkaline cleaning compositions,surprisingly, also works in an acidic cleaning composition.

According to the invention it was found that gluconic acid inhibitedcorrosion of stainless steel and nickel metal at approximately 25%active urea sulfate concentration at room temperature. The corrosionexhibited in stainless steel 316 and 304, the most common types used,after cleaning with the compositions of the invention was an average of0.1 mils per year, almost negligible levels. Further, the gluconic acidcompositions of the invention protected stainless steel and nickel fromcorrosion at a 1% solution of urea sulfate at 160° F. For stainlesssteels 316 and 304 the average corrosion rate was 0.03 mils per year,again almost negligible.

The compositions of this invention can be produced by first reactingurea and sulfuric acid and, optionally water, by either batch orcontinuous processes, to which the gluconic acid is later added. Whilenot wishing to be bound by any theory, it is postulated that thegluconic acid as well as other such acids which are intended to bewithin the scope of the invention, comprising a polyalcohol group atsimilar spacing of the carboxyl groups, coat the surface of the steel toprovide a protective coating which prevents the sulfuric acid fromcorroding the same, even in acidic environments.

DETAILED DESCRIPTION

So that the invention may be more readily understood, certain terms arefirst defined and certain test methods are described.

As used herein, “weight percent,” “wt-%,” “percent by weight,” “% byweight,” and variations thereof refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes acomposition having two or more compounds. It should also be noted thatthe term “or” is generally employed in its sense including “and/or”unless the content clearly dictates otherwise.

As used herein, the term “phosphate-free” refers to a composition,mixture, or ingredient that does not contain a phosphate orphosphate-containing compound or to which a phosphate orphosphate-containing compound has not been added. Should a phosphate orphosphate-containing compound be present through contamination of aphosphate-free composition, mixture, or ingredients, the amount ofphosphate shall be less than 0.5 wt %. More preferably, the amount ofphosphate is less then 0.1 wt-%, and most preferably, the amount ofphosphate is less than 0.01 wt %.

As used herein, the term “phosphorus-free” refers to a composition,mixture, or ingredient that does not contain phosphorus or aphosphorus-containing compound or to which phosphorus or aphosphorus-containing compound has not been added. Should phosphorus ora phosphorus-containing compound be present through contamination of aphosphorus-free composition, mixture, or ingredients, the amount ofphosphorus shall be less than 0.5 wt %. More preferably, the amount ofphosphorus is less than 0.1 wt-%, and most preferably the amount ofphosphorus is less than 0.01 wt %.

“Cleaning” means to perform or aid in soil removal, bleaching, microbialpopulation reduction, rinsing, or combination thereof.

As used herein, the term “ware” includes items such as eating andcooking utensils. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware.

The term “about,” as used herein, modifying the quantity of aningredient in the compositions of the invention or employed in themethods of the invention refers to variation in the numerical quantitythat can occur, for example, through typical measuring and liquidhandling procedures used for making concentrates or use solutions;through inadvertent error in these procedures; through differences inthe manufacture, source, or purity of the ingredients employed to makethe compositions or carry out the methods; and the like. The term aboutalso encompasses amounts that differ due to different equilibriumconditions for a composition resulting from a particular initialmixture. Whether or not modified by the term “about,” the claims includeequivalents to the quantities. All numeric values are herein assumed tobe modified by the term “about,” whether or not explicitly indicated.The term “about” generally refers to a range of numbers that one ofskill in the art would consider equivalent to the recited value (i.e.,having the same function or result).

In many instances, the terms “about” may include numbers that arerounded to the nearest significant figure.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5). According to the invention, application have created aphosphate free acid cleaning composition which may be used in place oftraditional phosphoric acid cleaning compositions, which retains thecleaning and anti-corrosive properties of the same and which isbiodegradable and less expensive to produce. The composition will finduse in any cleaning situation where phosphoric acid based cleaners canbe used, including, but not limited to, stainless steel.

Stainless steels are generally classified as carbon steels containing atleast about 5 weight percent, usually about 5 to about 40 weightpercent, and normally about 10 to about 25 weight percent chromium. Theymay also contain other alloying elements such as nickel, cerium,aluminum, titanium, copper, or other elements.

Stainless steels are usually classified in three differentcategories—austenitic, ferritic, and martensitic steels—which have incommon the fact that they contain significant amounts of chromium andresist corrosion and oxidation to a greater extent than do ordinarycarbon steels and most alloy steels.

Austenitic stainless steels or 300 series, make up about 70% percent ofstainless steel production and are the most common alloys of this group.They contain a maximum of 0.25% carbon, a minimum of 16% chromium andsufficient nickel and manganese to retain an austenitic structure at alltemperatures from the cryogenic region to the melting point of thealloy. For example type 309 has 0.20% chromium, type 310 has 0.25% andtype 314 has 0.25%. A typical composition of 18% chromium and 10%nickel, commonly known as 18/10 stainless, is often used in flatware.AISI types 302, 303, 304, and 316 are several of the more extensivelyused austenitic stainless steels.

Ferritic stainless steels are highly corrosion-resistant, but lessdurable than austenitic grades. They are generally characterized, inpart, by the fact that they contain chromium only (in addition to theother components of carbon steel) or only very minor amounts of alloyingelements. Martensitic stainless steels re not as corrosion-resistant asthe other two classes but are extremely strong and tough, as well ashighly machinable, and can be hardened by heat treatment. Martensiticstainless steel contains chromium (12-14%), molybdenum (0.2-1%), nickel(0-<2%), and carbon (about 0.1-1%) (giving it more hardness but makingthe material a bit more brittle). It is quenched and magnetic.

Stainless Steel Grades

The SAE steel grades are the most commonly used grading system in the USfor stainless steel.

100 Series—austenitic chromium-nickel-manganese alloys

-   -   Type 101—austenitic that is hardenable through cold working for        furniture    -   Type 102—austenitic general purpose stainless steel working for        furniture

200 Series—austenitic chromium-nickel-manganese alloys

-   -   Type 201—austenitic that is hardenable through cold working    -   Type 202—austenitic general purpose stainless steel

300 Series—austenitic chromium-nickel alloys

-   -   Type 301—highly ductile, for formed products. Also hardens        rapidly during mechanical working. Good weldability. Better wear        resistance and fatigue strength than 304.    -   Type 302—same corrosion resistance as 304, with slightly higher        strength due to additional carbon.    -   Type 303—free machining version of 304 via addition of sulfur        and phosphorus.    -   Type 304—the most common grade; the classic 18/8 stainless        steel.    -   Type 304L—same as the 304 grade but contains less carbon to        increase weldability. Is slightly weaker than 304.    -   Type 304LN—same as 304L, but also nitrogen is added to obtain a        much higher yield and tensile strength than 304L.    -   Type 308—used as the filler metal when welding 304    -   Type 309—better temperature resistance than 304, also sometimes        used as filler metal when welding dissimilar steels, along with        inconel.    -   Type 316—the second most common grade (after 304); for food and        surgical stainless steel uses; alloy addition of molybdenum        prevents specific forms of corrosion. It is also known as marine        grade stainless steel due to its increased resistance to        chloride corrosion compared to type 304. 316 is often used for        building nuclear reprocessing plants.^([13])    -   Type 316L—extra low carbon grade of 316, generally used in        stainless steel watches and marine applications due to its high        resistance to corrosion. Also referred to as “A4” in accordance        with ISO 3506.    -   Type 316Ti—includes titanium for heat resistance, therefore it        is used in flexible chimney liners.    -   Type 321—similar to 304 but lower risk of weld decay due to        addition of titanium. See also 347 with addition of niobium for        desensitization during welding.

400 Series—ferritic and martensitic chromium alloys

-   -   Type 405—ferritic for welding applications    -   Type 408—heat-resistant; poor corrosion resistance; 11%        chromium, 8% nickel.    -   Type 409—cheapest type; used for automobile exhausts; ferritic        (iron/chromium only).    -   Type 410—martensitic (high-strength iron/chromium).        Wear-resistant, but less corrosion-resistant.    -   Type 416—easy to machine due to additional sulfur    -   Type 420—Cutlery Grade martensitic; similar to the Brearley's        original rustless steel. Excellent polishability.    -   Type 430—decorative, e.g., for automotive trim; ferritic. Good        formability, but with reduced temperature and corrosion        resistance.    -   Type 439—ferritic grade, a higher grade version of 409 used for        catalytic converter exhaust sections. Increased chromium for        improved high temperature corrosion/oxidation resistance.    -   Type 440—a higher grade of cutlery steel, with more carbon,        allowing for much better edge retention when properly        heat-treated Type 446—For elevated temperature service

500 Series—heat-resisting chromium alloys

600 Series—martensitic precipitation hardening alloys

-   -   601 through 604: Martensitic low-alloy steels.    -   610 through 613: Martensitic secondary hardening steels.    -   614 through 619: Martensitic chromium steels.    -   630 through 635: Semiaustenitic and martensitic        precipitation-hardening stainless steels.        -   Type 630 is most common PH stainless, better known as 17-4;            17% chromium, 4% nickel.    -   650 through 653: Austenitic steels strengthened by hot/cold        work.    -   660 through 665: Austenitic superalloys; all grades except alloy        661 are strengthened by second-phase precipitation.

The acid cleaning compositions of the invention can be used in anyprocess that phosphoric acid cleaners have traditionally been used in,including but not limited to the stainless steel surfaces mentionedabove. The absence of thiol compounds makes this cleaning compositionacceptable for ware washing and cleaning of other surfaces that comeinto contact with food.

The composition of the invention will also find use in a number ofde-liming situations as well. In one embodiment the composition may beused on stainless steel pipes which need to use acid cleaners to de-limesurfaces including clean in place applications where the cleaner ispassed through the pipes. Other examples include vehicle cleaningapplications to replace sulfuric acid as a presoak prior to alkalinewashing solutions. Yet other examples include institutional waterstorage articles such as ice machines which need to be de-limed, in factthe compositions may be used in any situation where a surface needs tobe cleaned due to hard water residue. The solutions of the invention mayeven find use in the replacement of formic acid as a sour rinse fortextile processing, scale removal, manufacture of dyes and pigments forthe removal of excessive nitrite from diazotization reactions, in papermanufacturing by reducing pulp degradation in the bleaching stages ofelectroplating, and as a catalyst in urea-formaldehyde resinmanufacturing.

Gluconic acid is a mild organic acid formed by the oxidation of glucosewhereby the physiological d-form is produced. It is also called maltonicacid, and dextronic acid. It has the molecular formula C₆H₁₂O₇ andcondensed structural formula HOCH₂(CHOH)₄COOH. It is one of the 16stereoisomers of 2,3,4,5,6-pentahydroxyhexanoic acid. In aqueoussolution at neutral pH, gluconic acid forms the gluconate ion. Gluconicacid, gluconate salts, and gluconate esters occur widely in naturebecause such species arise from the oxidation of glucose. The chemicalstructure of gluconic acid consists of a six-carbon chain with fivehydroxyl groups terminating in a carboxylic acid group.

In aqueous solution, gluconic acid exists in equilibrium with the cyclicester Glucono delta lactone.

According to the invention, gluconic acid is added as a corrosioninhibitor to acid cleaning compositions. Applicants have found that theacid, traditionally used in alkaline solutions as a corrosion inhibitor,surprisingly works in an aqueous acid cleaning composition to inhibitcorrosion to almost negligible levels. It is postulated that otherpolyhydroxy carboxylic acids useful will contain from 4 to 10 carbonatoms, with similar location of the carbon atoms and similar polyolgrouping. Preferred is gluconic acid.

The present invention employs the use of gluconic acid as a corrosioninhibitor for use in acid cleaning compositions comprising preferablyurea and sulfuric acid, or urea sulfate. Typical urea sulfate acidcleaners contain from about 5 to about 85, preferably about 10 to about80 weight percent sulfuric acid; about 5 to about 75, preferably about10 to about 70 weight percent urea; and 0 to about 75, usually 0 toabout 50, and preferably 0 to about 25 weight percent water. Urea andsulfuric acid, in combination, constitute at least about 25, usually atleast about 50, and preferably at least about 75 weight percent of thecomposition, and are present in relative proportions corresponding tourea/sulfuric acid molar ratios of more than 2 or less than 1.

According to the invention, urea and sulfuric acid, in combination,constitute at least about 25, usually at least about 50, and preferablyat least about 75 weight percent of the composition, and are present inrelative proportions corresponding to urea/sulfuric acid molar ratios ofmore than 2 or less than 1.

Applicants have found that the level of gluconic acid to urea sulfatemust be at least greater than about 0.15% to 25% or a ratio of percentby weight of 0.012 to 1 of gluconic acid to urea sulfate. There isreally no upper limit on the amount of gluconic acid that can be addedto the solution, so long as the desired corrosion inhibition is achievedwith the acid cleaner. The solution could even have a greater gluconicacid content than urea sulfate. Not only does the gluconic acid protectthe surface of the metal from the sulfuric acid, it makes thecomposition less expensive and retains the anti-corrosive and cleaningproperties of phosphoric acid based cleaners. Applicants havesurprisingly found that addition of the corrosion inhibitor gluconicacid, which was thought to only work in alkaline cleaning compositions,instead works in an acidic cleaning composition.

According to the invention it was found that gluconic acid inhibitedcorrosion of stainless steel and nickel metal at approximately 25%active urea sulfate concentration at room temperature. The corrosionexhibited in stainless steel 316 and 304, the most common types used,after cleaning with the compositions of the invention, was an average of0.1 mils per year, almost negligible levels. Further, the gluconic acidcomposition of the invention protected stainless steel and nickel fromcorrosion at a 1% solution of urea sulfate at 160° F. For stainlesssteels 316 and 304 the average corrosion rate was 0.03 mils per year,again almost negligible.

The compositions of this invention can be produced by first reactingurea and sulfuric acid and, optionally water, by either batch orcontinuous processes, to which the gluconic acid is later added.

While not wishing to be bound by any theory, it is postulated that thegluconic acid as well as other such acids which are intended to bewithin the scope of the invention, comprising a polyalcohol group andsimilar spacing of the carboxyl groups, coat the surface of the steel toprovide a protective coating which prevents the sulfuric acid fromcorroding the same, even in acidic environments.

When the acid cleaning composition is used, the pH value of the usesolution should be below 5.

The aqueous solutions according to the invention may also contain othercomponents, if this appears to be desirable. In many cases it isadvisable to add surfactants in order to encourage a simultaneouscleaning and degreasing effect, and to ensure satisfactory wetting ofthe surfaces being treated with the acid cleaning composition. Thedesired amount of the surfactants may be added directly to the treatmentsolution, but it is preferable to add them to the concentrate used inproducing the solution.

In addition to the main components other additive may be added to thecompositions depending upon the soils to be removed, the stainless steelor other material to be cleaned, the requiring inhibiting affects, thedesired final surface properties and the waste disposal requirements andeconomic considerations. Other additives may also be included includingbut not limited to wetting agents to lower solution surface tension,solvents to aid in the removal of hydrophobic soils, defoamers toprevent foam or foam buildup on solution surface, thickeners (acidstable) to allow the cleaner to adhere (cling to vertical surface),passivators to protect the surface from environmental attack, andbiocides to control odor problems and kill harmful bacteria. Dyes, andother components may also be added.

The term “surfactant” or “surface active agent” refers to an organicchemical that when added to a liquid changes the properties of thatliquid at a surface.

Aesthetic enhancing agents such as colorants and perfume are alsooptionally incorporated into the concentrate composition of theinvention. Examples of colorants useful in the present invention includebut are not limited to liquid and powdered dyes from Milliken Chemical,Keystone, Clariant, Spectracolors, and Pylam.

Examples of perfumes or fragrances useful in concentrate compositions ofthe invention include but are not limited to liquid fragrances from J&ESozio, Firmenich, and IFF (International Flavors and Fragrances).

It should be understood that the water provided as part of the solutionor concentrate can be relatively free of hardness. It is expected thatthe water can be deionized to remove a portion of the dissolved solids.The concentrate is then diluted with water available at the locale orsite of dilution and that water may contain varying levels of hardnessdepending upon the locale. Although deionized is preferred forformulating the concentrate, the concentrate can be formulated withwater that has not been deionized. That is, the concentrate can beformulated with water that includes dissolved solids, and can beformulated with water that can be characterized as hard water.

Examples of useful ranges for the basic composition for the acidcleaning composition of the invention include those provided in thefollowing table:

Component Weight percent Weight percent Weight percent urea sulfate 1-90  1-50 15-40 gluconic acid 0.1-90 .1-50  .1-40

In an alternate embodiment, the cleaning compositions can be preparedaccording to the present invention include those provided in thefollowing table:

Component Weight percent Weight percent Weight percent urea 1-90 1-5015-40 sulfuric acid 1-90 1-50 10-35 gluconic acid 0.1-10  0.2-8   0.5-3 

The urea-sulfate/gluconic acid compositions of this invention can beproduced by the reaction of urea and sulfuric acid and, optionallywater, by either batch or continuous process with the addition ofgluconic acid and any other excipients thereafter.

Generally, the reaction products can be produced by separately andsimultaneously feeding urea, sulfuric acid, and optionally water, asrequired by stoichiometry, into a reacting liquid phase contained in areaction zone, in proportions corresponding to the relative proportionof each respective component in a predetermined product compositionwithin the ranges discussed herein. The urea and sulfuric acid reactwithin the reaction zone under controlled conditions in which reactiontemperature is always maintained at a point below about 176° F., andbelow the incipient decomposition temperature of the predeterminedproduct.

Use of acid cleaners may involve an alkaline clean with a detergentproduct and rinse, either prior to or after application of the acidcleaner and then a subsequent cold water rinse. In certain embodimentssuch as stainless steel cleaning, the final cold water rinse may befollowed with electroplating, chemical polishing, electropolishing, airblow drying, passivation treatments, neutralization treatments and thelike.

The invention has been shown and described herein in what is consideredto be the most practical and preferred embodiment. The applicantrecognizes, however, that departures may be made therefrom within thescope of the invention and that obvious modifications will occur to aperson skilled in the art. The examples which follow are intended forpurposes of illustration only and are not intended to limit the scope ofthe invention. All references cited herein are hereby incorporated intheir entirety by reference.

EXAMPLES Metal Corrosion Test

The following test method describes an accepted, but not exclusive,procedure for metal corrosion testing as outlined in the AmericanSociety for Testing and Materials (ASTM), Volume 3.02, G31-72 and 3.02,G1-90, and as outlined in the Klenzade Good Laboratory Practice standardtest method, K004-01-01, which is in compliance with EnvironmentalProtection Agency (EPA) registration and UN/DOT for corrosion testing.This test method was employed in Examples 2 and 3.

Metal strips are pre-cleaned, weighed, and put into glass bottles withproduct solution (100% concentration for UN/DOT) and placed atappropriated temperature (130° F. (54.5° C.) for UN/DOT). After thespecified time, the corroded metal strips are then cleaned, weighed, andweight loss is determined. Corrosion rates are directly proportional tothe mass loss of the metal strip and inversely proportional to the striparea, density, and time of exposure to the test solution. A corrosionrate exceeding 250 mpy is classified as UN/DOT corrosive to the testmetal.

Metal Strip Preparation—Pre-Cleaning

-   1. Identify each metal strip by using steel tencil stamp. Prepare at    least duplicates per test condition and metal type, and duplicate    controls per metal type being tested.-   2. Pre-clean all metal strips.-   3. Clean soft metals such as galvanized steel (zinc), aluminum,    brass, copper, and nickel with detergent (EXPRESS) and a soft    sponge. Then, ultrasonic clean in toluene for 30 minutes. Scrubbing    with an abrasive powder and a pad can mar the surface, increasing    surface area which could increase corrosion results.-   4. To clean hard metals, such as cold rolled steel 1018 and    stainless steel 304 y 316, scrub with bleach-free scouring powder,    Bon Ami.-   5. Rinse metal strips with distilled water followed with an acetone    rinse.-   6. Let metal strips air dry. Store strips in desiccator until used.    Aluminum and copper should be stored a minimum of 24 hours in a    desiccator before testing to allow protective coatings to reform on    the test panel surface.-   7. Weigh the clean, dry, metal strips and controls (precleaning    weight) on an analytical balance. EPA GLP work must be weighed on an    approved balance.

Test Conditions

-   1. Determine temperature desired for testing. Temperature of testing    is generally ambient (68-72° F.) for EPA GLP or 130° F. for UN/DOT.-   2. Label containers. The standard container is a one-liter,    wide-mouth glass jar. Test metal strips should be supported in the    standard container so that the metal strip is no less than 45    degrees relative to the horizontal plane. Glass panels are inserted    vertically in the standard container as a support with the metal    strip resting against it with as little contact as possible to    obtain this angle.-   3. Make desired test concentrations. Solutions should be made on a    percent by weight basis. For UN/DOT testing, product is undiluted,    100% concentration. Test volume should be approximately 125 ml per    square inch of metal strip surface area, i.e., a 1″×3″ metal strip    requires 750 ml of test solution; a 0.5″×4″ metal strip requires 500    ml of test solution.-   4. The length of exposure should be determined using the following    guideline:

Number of hours=2000/mpy (estimated)

-   -   Typically, the exposure time is not less than eight hours or        longer than 168 hours. For UN/DOT testing, standard time is        eight hours.

Test Procedure

-   1. Preheat water bath if necessary.-   2. Preheat test solution to test temperature.-   3. Pour desired test concentration, as determined by Step 3 in Test    Conditions section, per size of metal strip into standard    containers. Put strips in test solution, apply caps. Controls are    not exposed to either test solution or water. See step 2 in Cleaning    Metal Strips After Testing—Post-Cleaning Section.-   4. At the end of test time, remove metal strips from the container    and rinse with distilled water.    Cleaning Metal Strips after Test—Post-Cleaning-   1. The metal strips are chemically cleaned to remove the corroded    metal from the surface by dissolution in an appropriated chemical    solution. See Table 1 attached to determine time, temperature, and    solution to use. After metal strips are exposed to the appropriated    chemical solution, rinse with distilled water, followed by an    acetone rinse. Let air dry. Analytically weigh metal strips    (post-cleaning weight).-   2. At the same time the test strips are post-cleaned, the controls    are also post-cleaned in the appropriated chemical solution per    metal type. An ideal procedure should remove only corroded metal,    not base metal. To determine the mass loss of the base metal, the    controls are post-cleaned. Analytically weigh controls. This weight    loss by the control strips is the cleaning weight loss (CWL).

Calculations

-   1. Calculate the total weight loss (TWL) for each test strip.

TWL=Pre-cleaning weight−Post-cleaning weight

-   2. Calculate the cleaning weight loss (CWL) experienced by the    control strips per metal type tested.

CWL=Pre-cleaning weight of controls−Post cleaning weight of controls

-   3. Calculate the adjusted weight loss (AWL).

AWL=TWL−CWL

-   4. Calculate the corrosion rate in mils per year (mpy) for each    strip.

mpy=(534,000*AWL)/(A*T*D)

-   -   A=area in inches squared (6 sides)        -   i.e., 1″*3″* 1/16″=        -   2(1*3)+2(0.0625*1)+2(0.0625*3)=        -   6+0.125+0.375=        -   6.5 inches squared        -   i.e., 0.5″*4″*⅛″=        -   2(0.5*4)+2(0.125*0.5)+2(0.125*4)=        -   4+0.125+1=5.125 inches squared    -   T=Time exposure (hours)    -   D=Metal density (g/cm3)    -   AWL=Adjusted weight loss (grams)

-   5. Calculate the average corrosion rate for each set of metal    strips. A product causing a corrosion rate larger than 250 mpy is    considered corrosive to that specific metal by DOT and the UN.

TABLE 1 PRE- POST-CLEANING METHOD DIMENSION MLS TEST CLEANING TIME TEMPDENSITY HEIGHT WIDTH THICK AREA SOLUTION METAL METHOD Min. ° F. SOLUTIONg/cc In In In In² ml ALUMINUM 7075 SOFT 3 ROOM CONC HNO₃ 2.81 3 1 0.06256.5 750 TEMP BRASS B380, 7030 SOFT 3 ROOM 1:1 CONC HCI/H20 8.5 3 10.0625 6.5 750 TEMP COPPER SOFT 3 ROOM 1:1 CONC HCI/H20 8.96 3 1 0.06256.5 750 TEMP C.R. STEEL 1018 HARD 3 ROOM 1000 ml CONC HCI 7.86 4 0.50.125 5.125 500 TEMP 20 g ANTIMONY TRIOXIDE (Sb₂O₃) 50 G STANNOUSCHLORIDE (SnCl₂) GALVANIZED SOFT 5 ROOM 100 G AMMONIUM 8.78 3 1 0.03756.3 750 STEEL (ZINC) TEMP PERSULFATE/1 L G90-LFQ-RSCT ((NH₄)₂S₂O₈)NICKEL 200 SOFT 3 ROOM 150 G HCI/1 L 8.89 3 1 0.0625 6.5 750 TEMP SS304, BRUSHED #4 HARD 20 70° C./ 150 g DIAMMONIUM 7.94 3 1 0.0625 6.5 750158° F. CITRATE/11 ((NH₄)₂HC₆H₅O₇) SS 316, BRUSHED #4 HARD 20 70° C./150 g DIAMMONIUM 7.98 3 1 0.0625 6.5 750 158° F. CITRATE/11((NH₄)₂HC₆H₅O₇)

Example 2 Project: Urea Sulfate Corrosion Begin Urea Sulfate+GluconicAcid Corrosion Test

1 L of an acid cleaning solution of urea sulfate+gluconic acid solutionwas made for testing corrosion

weight % 715.4 71.54 Water 166.6 16.66 H2SO4 93% 115.0 11.50 Urea Prill3.0 0.30 Gluconic acid 50% 1000.0 100.00

-   One coupon each of Ni, 304SS, 316SS, 410SS were tested. Each coupon    was placed in an 8 oz glass bottle and submerged with ˜200 mL    concentrated urea sulfate+gluconic acid solution. The bottles were    then placed in a preheated water bath at set at 160° F.-   Next one coupon each of Ni, 304SS, 316SS, 410SS were tested by    placing 2 drops concentrated urea sulfate+gluconic acid solution on    top of coupon near the middle and the coupons were let sit at room    temp. No obvious initial reaction between solution and any of the    coupons was observed.-   The 410SS and 304SS coupons were removed from water bath after one    hour and 15 minutes because both failed. The solutions were green    with lots of bubbles forming in bottles.-   Next 300 mL of urea sulfate+gluconic (2×) acid was made and a test    began for the 410SS in water.

213.7 71.24 Water 50.0 16.66 H2SO4 93% 34.5 11.50 Urea Prill 1.8 0.60Gluconic acid 50% 300.0 100.00

Corrosion Test:

Later the 410SS coupon was removed from bath in morning because offailure, the solution was green and coupon was paper thin (most wascorroded away).

The 316SS and Ni coupons were removed from the bath at 24 hours. The316SS coupon solution was light green with slight bubble formation inbottle. The Ni coupon solution was observed to be slight yellow withvery slight bubble formation.

The coupons were then rinsed at room temperature with deionized waterand blotted dry. None of the coupons showed any evidence of corrosion,all were still shiny.

Example 3 Urea Sulfate+Gluconic Acid Corrosion Test Preparation

Coupons were weighed and measured coupons for compatibility testing perthe table below.

Ni surface Initial depth area (SA) weight coupon length (in) width (in)(in) (in{circumflex over ( )}2) (g) 100% 1 3.006 1.000 0.063 6.51727.1555 solution 2 3.015 1.003 0.062 6.546 27.1332 3 3.004 1.001 0.0626.511 26.8191 Initial depth weight coupon length (in) width (in) (in) SA(in{circumflex over ( )}2) (g) 316SS 100% 1 3.003 0.997 0.060 6.46823.1391 solution 2 3.003 0.998 0.060 6.474 23.1836 3 3.002 0.996 0.0606.460 23.1484 304SS 100% 1 3.002 0.999 0.058 6.462 22.2192 solution 23.011 0.998 0.058 6.475 22.2454 3 3.010 0.999 0.058 6.479 22.2686 410SS100% 69 3.006 1.004 0.050 6.437 19.0677 solution 70 3.006 1.005 0.0506.443 19.0878 71 3.004 1.006 0.050 6.445 19.0685

Urea Sulfate+Gluconic Acid Room Temp Corrosion Test:

24 L of urea sulfate+gluconic acid solution was prepared for corrosiontesting.

1717.0 71.54 water 399.8 16.66 H2SO4 93% 276.0 11.50 prilled urea 7.20.30 gluconic acid 50% 2400.0 100.00˜200 mL was poured in each 8 oz. glass bottles with respective cleanedcoupons as detailed below.

The Nickel coupon was cleaned with mild detergent then sonicated intoluene for 30 min. before rinsing with acetone. The stainless steelcoupons were cleaned with Bon Ami and rinsed with acetone. The bottleswere set at room temp to begin test at 10:00 a.m. By 2:00 p.m., 410SScoupons failed (solution green with bubble formation).

End Urea Sulfate+Gluconic Acid Room Temp Corrosion Test:

The metal corrosion test was ended at 10:00 am after 24 hours. Allcoupons were removed from bottles. The 410SS coupons failed, all otherswere rinsed with deionized water.

The coupons were cleaned. The nickel coupons were placed in a 200 mL HCLsolution for 3 min. at room temp (150 gHCL:1 L deionized water), rinsedwith deionized water, then acetone. The stainless steel coupons wereplaced in a 200 mL diammonium citrate solution (150 g diammoniumcitrate:1 L DI water) for 20 min. at 70° C., rinsed with deionizedwater, then acetone.

The coupons were then weighed and mils per year (mpy) were calculatedfor each.

final final coupon weight (g) TWL (g) mpy observations Ni 100% 1 27.15460.0009 0.3457 no change solution 2 27.1312 0.0020 0.7646 no change 326.8193 −0.0002 −0.0769 no change 316SS 100% 1 23.1392 −0.0001 −0.0431no change solution 2 23.1835 −0.0001 0.0431 no change 3 23.1486 −0.0002−0.0863 no change 304SS 100% 1 22.2192 0.0000 0.0000 no change solution2 22.2459 −0.0005 −0.2164 no change 3 22.2691 −0.0005 −0.2163 no change410SS 100% 69 failed — — green solution, solution black coupons 70failed — — green solution, black coupons 71 failed — — green solution,black coupons

Urea Sulfate+Gluconic Acid Room Temp Use Solution Corrosion Test—

600 mL of urea sulfate+gluconic (2×) acid (4% solution) was made forcorrosion testing

593.10 98.85 water 4.00 0.67 H2SO4 93% 2.76 0.46 prilled urea 0.14 0.02gluconic acid 50% 600.0 100.00

One each of Ni, 304SS and 316SS coupons was cleaned. The Ni coupon wascleaned with mild detergent, and then sonicated in toluene for 30 minbefore rinsing with acetone. The stainless steel coupons were cleanedwith Bon Ami and rinsed with acetone. Approximately 200 mL was poured in8 oz glass bottles with respective cleaned weighed coupons.

Coupon Wt(g) Ni 26.7992 304SS 22.4941 316SS 23.1141

-   -   All coupons were removed from bottles and rinsed with deionized        water.

The coupons were cleaned again per the post cleaning method. The nickelcoupon was placed in 150 mL HCL solution at room temp for 3 min., rinsedwith deionized water, then acetone. The stainless steel coupons wereplaced in 150 mL diammonium citrate solution at 70° C. for 20 min.,rinsed with deionized water, then acetone. The coupons were weighed andthe mils per year (mpy) were calculated for each. The solutions with316SS and 304SS had slight bubble formation.

final final coupon weight (g) TWL (g) mpy observations Ni 4% solution 126.7945 0.0047 1.8108 no change 316SS 4% solution 1 23.1148 −0.0007−0.3012 no change 304SS 4% solution 1 22.4945 −0.0004 −0.1734 no change

End Urea Sulfate+Gluconic Acid Temp 160° F. Solution Corrosion Test—:

At the end of the test, all coupons were removed from the bottles andrinsed with water. The coupons were cleaned. The nickel coupon wasplaced in 150 g HCL solution at room temp for 3 min., rinsed with DIwater then acetone. The stainless steel coupons were placed in 150 mLdiammonium citrate solution at 70° C. for 20 min., rinsed with DI water,then acetone. The coupons were weighed and mpy was calculated for each.

final final coupon weight (g) TWL (g) mpy observations Ni 4% solution 126.7715 0.0230 8.8616 slt white film 316SS 4% solution 1 23.1152 −0.0004−0.1721 no change 304SS 4% solution 1 22.4946 −0.0001 −0.0434 no change

1: An aqueous acid cleaning composition with a pH of less than 7 andcomprising sulfuric acid urea, water, and corrosion inhibiting amount ofgluconic acid, wherein said urea and sulfuric acid have a molar ratio ofabout 1 to 2 to create urea sulfate.
 2. (canceled) 3: The composition ofclaim 2 wherein said gluconic acid to urea sulfate is at least about0.012% to 25% by weight of the solution. 4: The composition of claim 2wherein said about 5 to about 75 weight percent urea, about 5 to about85 weight percent sulfuric acid, and about 0 to about 75 weight percentwater. 5: The composition of claim 4 wherein the urea/sulfuric acidmolar ratio is greater than 2 or less than
 1. 6: The composition ofclaim 4 wherein a portion of said urea and sulfuric acid are present asa member selected from the group consisting of monourea sulfate, diureasulfate, and combinations thereof. 7: The composition of claim 1comprising about 25% by weight urea sulfate and about 0.60 percent byweight of gluconic acid (50%). 8: The composition of claim 7 whereinsaid 25% by weight of urea sulfate comprises about 16% sulfuric acid(93%) and 11% urea. 9: The composition of claim 7 wherein said sulfuricacid (93%) is in an amount of 16.66%. 10: The composition of claim 9wherein said urea is in an amount of about 11.50% by weight of solution.11: The composition of claim 9 wherein water comprises about 70% of saidsolution. 12: The composition of claim 7 comprising the followingcomponents: sulfuric acid about 17% urea about 11% gluconic acid about0.60% with the remainder being water. 13: The composition of claim 12comprising the following: water 71% sulfuric acid 16.5% urea 11.5gluconic acid 0.60 14: The composition of claim 1 further comprising oneor more of the following: a dye, a sequestrant, a defoamer, or apreservative. 15: A method of producing an aqueous urea sulfate acidcleaning composition comprising: combining urea and sulfuric acid in amolar ratio of 1 to 2 in the presence of water so that an aqueoussolution of monourea sulfate, diurea sulfate, and combinations thereofare formed, adding to said aqueous solution a corrosion inhibitingamount of gluconic acid. 16: A biodegradable, acid cleaning compositioncomprising the following: water 71% sulfuric acid 16.5% urea 11.5%gluconic acid 0.60%, wherein said urea and sulfuric acid have a molarratio of about 1 to 2 to create urea sulfate. 17: The cleaningcomposition of claim 16 further comprising: one or more of thefollowing: a defoamer, a sequestrant, or a preservative.